Locally Induced Spin States on Graphene by Chemical Attachment of

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Locally Induced Spin States on Graphene by Chemical Attachment of Boron Atoms Qing Li,† Haiping Lin,*,† Ruitao Lv,‡ Mauricio Terrones,§,∥,⊥,▽ Lifeng Chi,† Werner A. Hofer,*,# and Minghu Pan*,○

Nano Lett. Downloaded from pubs.acs.org by UNIV OF SUNDERLAND on 08/31/18. For personal use only.

†

Institute of Functional Nano and Soft Materials (FUNSOM) & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, China ‡ Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China § Department of Chemistry, Department of Materials Science and Engineering and Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, University Park, Pennsylvania 16802, United States ∥ Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano, 380-8553, Japan ⊥ Department of Materials Science and Engineering & Chemical Engineering, Carlos III University of Madrid, Avenida Universidad 30, 28911 Leganés, Madrid, Spain ▽ IMDEA Materials Institute, Eric Kandel 2, Getafe, Madrid 28005, Spain # School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, United Kingdom ○ School of Physics, Huazhong University of Science and Technology, Wuhan 430074, China S Supporting Information *

ABSTRACT: Pristine graphene is known to be nonmagnetic due to its π-conjugated electron system. However, we find that localized magnetic moments can be generated by chemically attaching boron atoms to the graphene sheets. Such spin-polarized states are evidenced by the spin-split of the density of states (DOS) peaks near the Fermi level in scanning tunneling spectroscopy (STS). In the vicinity of several coadsorbed boron atoms, the Coulomb repulsion between multiple spins leads to antiferromagnetic coupling for the induced spin states in the graphene lattice, manifesting itself as an increment of spin-down state at specific regions. Experimental observations and interpretations are rationalized by extensive density functional theory (DFT) simulations.

KEYWORDS: Graphene, STM, STS, spin, DFT Despite several attempts of removing pz orbitals in πconjugated carbon systems, either by creating atomic vacancies or by chemically doping graphene with heteroatoms,3−5,10−18 local magnetic states at the atomic scale were not reported until very recently by Brihuega et al.8 In these experiments the chemisorption of single hydrogen atoms on graphene was observed to induce a magnetic moment of 1 μB, and the polarized states were evidenced by the characteristic split of resonance peaks. Following on from their pioneering study, two key issues remain unclear: (1), whether heavier dopants would produce a larger moment per adsorption site; and (2), whether these magnetic moments interact between multiple adsorption sites. In this article, we show that localized

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hile pristine graphene is known to be intrinsically nonmagnetic due to its π-conjugated electron system,1 2 Lieb proposed that the ground state of graphene may possess a total spin given by S = 1/2 × |NA − NB|, where NA and NB are the number of pz orbitals removed from each triangular sublattice. Single magnetic states close to the Fermi energy (EF) can therefore be induced by removing pz orbitals from one of the carbon sublattices.3−7 As the double occupation of such a magnetic state by two electrons with different spins is hindered due to the Coulomb repulsion, an energy split can be observed near the Fermi energy, with the energy difference being determined by the strength of Coulomb repulsion U.8 However, the removal of the pz orbital may not necessarily result in net magnetism,8,9 as magnetic moments can only be induced if the strength of the Coulomb repulsion U is significantly larger than the energy width Δ of the split states (πΔ/U < 1). © XXXX American Chemical Society

Received: May 9, 2018 Revised: July 19, 2018 Published: August 16, 2018 A

DOI: 10.1021/acs.nanolett.8b01798 Nano Lett. XXXX, XXX, XXX−XXX

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Figure 1. STM images and DFT simulations of the single substitutional boron dopant. (a) Large-area STM image of the synthesized BG sheet on SiO2/Si, with Vb = −700 mV and Is = 50 pA. The raw STM image was digitally flattened by removing the overall roughness of the substrate. The inset shows the corresponding FFT pattern. (b) High-resolution STM image for single boron substitutional dopant 1B (upper) and a height profile measured across such dopant (lower). (c) Structural model (left) and corresponding DFT simulation (right) of graphene with a substitutionally doped boron atom. (d) dI/dV spectrum of the substitutional dopant 1B. (e) Calculated spin-DOS of the single substitutional boron-doped graphene.

STS measurements were performed on BG sheets after transfer onto the SiO2/Si substrates. A large-area scan shows a surface with corrugations of 0.6−1.0 nm, which can be attributed to the roughness of the SiO2/Si substrate. This roughness leads to difficulties in the identification of boron atoms, compared to graphene on a flat substrate.8 We therefore flattened the raw data by subtracting the background roughness. As shown in Figure 1a, the carbon honeycomb lattice is decorated with numerous protrusions. Since these protrusions are absent in pristine graphene, we identify them as boron dopants. The fast Fourier transform (FFT) image presented in the inset of Figure 1a exhibits the typical reciprocal hexagonal symmetry of the graphene lattice (outer hexagon) and the intervalley scattering peaks (inner hexagon), representing the enhanced electron scattering induced by the B-defect. Different from the well-studied nitrogen doped graphene,23−26 boron dopants have been much less researched.24,27−29 Figure 1b shows an STM image on which a single protrusion is observed. A line profile across such protrusions shows an apparent height of 0.5 Å. DFT simulations reveal that it is a single substitutionally doped boron atom (referred to as “1B”, as shown in Figure 1c) and the calculated corrugation is about 0.7 Å, in good agreement with the experimental observations. The STS

magnetic moments can be induced in the graphene lattice by the chemisorption of boron atoms. Each boron atom gives rise to a magnetic moment of 2.8 μB, which is much larger than the moment due to an adsorbed hydrogen atom. 8 More importantly, antiferromagnetic coupling between the induced spins is observed, giving rise to an increment of spin-down states in specific locations. Boron doped graphene (BG) sheets were synthesized using ambient-pressure chemical vapor deposition (CVD), the details of the sample preparation can be found in the Methods part of the Supporting Information. The identity of boron atoms is confirmed by X-ray photoelectron (XPS) and Raman spectroscopy (Details of the XPS characterization can be found here19). For B-doped graphene, two prominent peaks located at 186.4 and 190.3 eV are identified in the B 1s line scans.19 The peak of 190.3 eV, can be assigned to the substitutional boron atoms embedded within the graphene lattice.20,21 A Bader analysis shows that the chemisorbed boron carries less positive charge (+1 |e|) compared to the substitutional boron (+3 |e|). As a consequence, the binding energy of the chemisorbed boron is less than that of the substitutional boron. Therefore, the peak located at ∼186.4 eV in the XPS spectra can be assigned to the chemisorbed boron.22 STM/ B

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Figure 2. STM image and DFT simulations for a chemisorbed boron atom. (a) High-resolution STM image for chemisorbed boron atoms. Vb = −700 mV, and It = 50 pA. Inset: A height profile measured along the blue dashed line across the protrusion. (b) dI/dV spectrum measured on the site of the chemisorbed boron atom. (c) Structural model (upper) and DFT simulation (lower) of the single chemisorbed boron atom. (d) Top (upper) and side views (lower) of the spatial distribution of the calculated spin-up (red) and spin-down (blue) DOS. (e) Calculated spin-polarized density of states of the single chemisorbed boron.

the spectra on carbon vacancy defects,30 and on hydrogen adsorbates,8 we attribute the feature to an impurity-induced magnetic resonance. It is also worth noting that the Dirac point Ed varies with the spatial locations, originating from the local inhomogeneity of doping, which is more prominent for CVDgrown graphene. We have obtained various spectra with different Dirac point energies Ed over the studied surface, as shown in Figure S2. Note that the peak splitting remains unaltered within the error bar. According to the Anderson impurity model in which a single electronic state is attached to the host graphene state, the energy of the localized states can be written as E↑ = ED − Un↓ and E↓ = ED+Un↑, where n is the occupation of each of the two spin states, ED is the energy of the Dirac point, and U is the strength of the Coulomb repulsion, which can be determined by the splitting of the magnetic peaks.9,31 For the chemisorbed single boron atom, U is measured to be 63 meV, which is much larger than that of a hydrogen atom.8 Additional differences are that the chemisorption of H atoms leads to spin-split peaks with n↑ = 1, n↓ = 0, and where ED is below the Fermi energy. In our case, ED is located at +7 meV, slightly above EF, which might be due to a shift of the local Dirac point, induced by the boron doping. The introduction of magnetic states via boron chemisorption is further evidenced by DFT calculations. The spin-polarized density of states (spin-DOS) of the single chemisorbed boron atom on the graphene lattice is shown in Figure 2e (the calculated spin-DOS with a wider energy

acquired on a single boron dopant shows an overall U-shaped curve with no obvious feature near the Fermi level, implying no pz orbital being removed upon substitutional-doping (Figure 1d). The conclusion is further confirmed by DFT calculations, which show that the spin-up and spin-down component of the DOS of the substitutionally doped boron atom is fully compensated (Figure 1e), leading to a net magnetism of 0 μB. This can be understood from the fact that the electrons from boron atoms are embedded in the graphene lattice, so that the conjugation of pz orbitals over the atomic plane of graphene is not affected. Other types of substitutional boron dopants were also investigated by both STM/STS and DFT calculations, all give a zero magnetic moment (see Supporting Information, Figure S1, for details). By contrast, the situation for chemisorbed boron atoms is completely different. Figure 2a gives much brighter protrusions, the apparent height now is about 1.3−1.6 Å above the carbon lattice. According to our DFT modeling and STM image simulation (Figure 2c), single boron atoms prefer to attach at the bridge sites of graphene, with an apparent height of 1.8 Å. More intriguingly, the DOS (measured at 4.2 K) acquired on the chemisorbed atoms exhibit a distinct peak located at +7 meV and a weak shoulder at +70 meV (Figure 2b), which differs significantly from the substitutional case. No prominent feature is observed at the Fermi level in the region far away from the adsorbates. Considering the similarities between the STS spectrum of the chemisorbed boron atom, C

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Nano Letters window is provided in Figure S3). For comparison, the calculated spin-DOS of the vacancies in graphene lattice is provided in Figure S4, in which a localized spin is observed. Both, the prominent DOS peak for the spin-up component and the weak DOS peak for spin-down component appear near EF, giving a total induced magnetic moment of 2.8 μB. DFT calculations reveal that the spin-polarized electronic states are mostly localized around the adsorbed boron atom, as shown in Figure 2d. Different from the chemisorbed H that sits at the on-top site of carbon, the boron atom prefers to adsorb at the bridge site between two adjacent carbon atoms. Correspondingly, the spin-split states are in evidence on both of the two adjacent carbon atoms. Since these two carbon atoms belong to different graphene sublattices, the spin-split states are created in both sublattices and propagate along their respective sublattices, as shown in Figure 2d. To confirm the spatial distribution of the magnetic states, a series of dI/dV spectra was recorded along a dashed line across a boron adsorbate at equal separations of 1 Å (Figure 3a). Here, we

( x)

via an empirical formula, exp − L [∑ FuncPeak (x − xc)]. Here, x is the tip displacements, xc is the lateral position of intensity maxima, and L is the decay length. Func is a series of Gauss peaks with various peak positions. The decay length is then calculated to be about 1.5 nm by fitting the peak intensity. The periodicity is different along different directions. For example, as shown in Figure S5, the dI/dV spectra along the zigzag direction have a periodicity of 2.8 ± 0.2 Å, close to the atomic separation along the zigzag direction of the carbon lattice (2.56 Å). It is noteworthy that the adsorption of boron atoms at the bridge site does not break the sublattice symmetry of graphene, which is different from previous reports.2,8 In fact, a boron adatom will induce spin polarization in both sublattices and propagate in each sublattice individually. As a single chemisorbed boron atom can induce spin polarization in surrounding electrons, it is of particular interest to study the interaction of the spin states induced by multiple boron adsorptions. Figure 4a shows an STM image of a region that includes multiple chemisorbed boron atoms. Figure 4b gives three representative dI/dV spectra taken at different positions in Figure 4a. The spectrum acquired above the boron atom (red dot and red curve), shows a dominant peak located at +7 meV and a weak shoulder at +70 meV, the spectrum acquired in the middle area exhibits two split peaks with comparable intensities (blue curve), while at the positions of black dots the spectrum exhibits a dominant peak at +70 meV and a weak shoulder at +7 meV (black curve). To further investigate the spatial distributions of the spin-split peaks, a series of dI/dV spectra (Figure 4c) were taken along the black dashed line given in Figure 4a. The spin-split peaks are always observed, and the peak positions remain unchanged, while the relative intensity varies spatially. This phenomenon can be further scrutinized by conductance maps, as shown in Figure 4a. The dI/dV image acquired at +7 meV exhibits four distinct protrusions, corresponding to the four adsorbed boron atoms. At the energies of +70 meV, the DOS above these adsorbed boron atoms is suppressed. By contrast, the DOS is substantially enhanced along the sides of the triangle defined by the black dots. According to previous reports,8 the spin-split peaks are a result of Coulomb repulsion between electrons of different spins. The intensity of the +7 and +70 meV peaks therefore represents the level of spin-up and spin-down occupation, respectively. The occupation of spin-down states is negligible at boron adsorbates (Figure 3b), whereas it is enhanced within the boron triangle. The enhancement of the spin-down component can only be a result of the Coulomb interaction between multiple spins. This interaction between multiple spins is akin to a “pseudo-antiferromagnetic” spin interaction for induced spin states. To clarify the effect, a spin intensity map was calculated numerically, based on the assumption of antiferromagnetic interaction between the induced spin states generated by the three boron atoms; it is shown in Figure 4d. The spin intensity maps are in good agreement with the maps shown in Figure 4a, and they show a periodic variation of the spin amplitudes. In a nonmagnetic system, similar effects can be observed for the electron densities, for example in a quantum corral on silver.32 It is therefore tempting to think of the area enclosed by the boron adsorbates as a similar type of corral, only in this case a spin quantum corral. In summary, we report that localized magnetic moments can be generated by chemically attaching boron atoms on CVD

Figure 3. Propagation of spin-split states in the graphene lattice. (a) Highly resolved STM image for a single chemisorbed boron atom. Vb = −700 mV, and It = 50 pA. The image size is about 0.9 × 6.5 nm2. The lower panel illustrates the propagation of the induced spin state. (b) A series of dI/dV spectra recorded along the black dashed line in part a with a distance separation of 1 Å. The dI/dV spectra are superimposed with the colored differential conductance map. The position of the boron atom is indicated by a yellow arrow. (c) Distribution of the intensities of the +7 meV peak with the tip displacements. Inset: Direction of the tip displacements. The blue dashed line is the fitting curve. The position of the boron atom is indicated by the black dashed arrow.

only extract the intensity of the peak located at +7 meV since it is much stronger than that at +70 meV. From both, the differential conductance map (Figure 3b) and the extracted peak intensity (Figure 3c) plotted with respect to the lateral tip displacements, a slow decay of the resonances is in evidence, accompanied by a periodic oscillation. The periodicity of the spatial distribution of the magnetic states is 0.62 nm, corresponding to the atomic separation of one sublattice orientated 18° deviated from the zigzag direction (Figure 3c). Such a propagation of spin-split states can be well reproduced D

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Figure 4. Spin interactions from multiple boron adsorbates. (a) From top to bottom, respectively: topographic image (four chemisorbed boron atoms indicated by the shadowed circles), conductance map acquired at +7 meV and conductance map acquired at +70 meV. Images are obtained at 4.2 K. (b) Three representative dI/dV spectra measured at the sites indicated in (a), showing the spin-up dominance, spin-down dominance and the coexistence of comparable spin states, respectively. (c) Series of dI/dV spectra recorded along the black dashed line shown in part a equally separated by 1 Å. The spectra acquired on the top of boron atoms are indicated with yellow arrows. (d) Calculated spin intensity distributions based on the assumption of antiferromagnetic interaction among adjacent induced spins. The positions of boron atoms are indicated by the golden balls.

prepared graphene sheets. The magnetism arises from the removal of local pz orbitals from the carbon sublattices by the chemisorption of boron atoms. The magnetic polarization is characterized by the splitting of the resonance peaks close to the Fermi level, which is experimentally evidenced by STS measurements. These spin-split states extend 1.5 nm over the surface. In the vicinity of several coadsorbed boron atoms, the Coulomb repulsion between multiple spins leads to antiferromagnetic coupling for the induced spin states in the graphene lattice, manifesting itself as a redistribution of the spin-up and spin-down state occupation, which can be interpreted as a “quantum spin corral”.

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Lifeng Chi: 0000-0003-3835-2776 Werner A. Hofer: 0000-0002-1305-4716 Minghu Pan: 0000-0002-1520-209X Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge the Collaborative Innovation Center of Suzhou Nano Science & Technology and the Priority Academic Program Development of Jiangsu Higher Education Institutions. This work is supported by the National Natural Science Foundation of China (91545127, 21622306, 21771134, 51722207, 51372131, 11574095), the National Major State Basic Research Development Program of China (2017YFA0205002, 2014CB932600), and the Natural Science Foundation of Jiangsu Province (BK20150305). M.T. thanks the Army Research Office (W911NF-16-1-0019) and the National Science Foundation (2DARE-EFRI 1542707). W.A.H. acknowledges EPSRC funding for the UKCP consortium (EP/K013610/1).

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.nanolett.8b01798.

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Details of the sample preparation, STM/STS measurements and the DFT calculations, various kinds of dopants and their electronic structures, and spin-DOS of the carbon vacancy (PDF)

AUTHOR INFORMATION

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Corresponding Authors

*(H.L.) E-mail: [email protected]. *(W.A.H.) E-mail: [email protected]. *(M.P.) E-mail: [email protected].

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ORCID

Haiping Lin: 0000-0002-9948-7060 Ruitao Lv: 0000-0002-3214-9489 E

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